CN103228601A - Method for the production of a phenylcyclohexane - Google Patents
Method for the production of a phenylcyclohexane Download PDFInfo
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- CN103228601A CN103228601A CN2011800574937A CN201180057493A CN103228601A CN 103228601 A CN103228601 A CN 103228601A CN 2011800574937 A CN2011800574937 A CN 2011800574937A CN 201180057493 A CN201180057493 A CN 201180057493A CN 103228601 A CN103228601 A CN 103228601A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/10—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of aromatic six-membered rings
- C07C5/11—Partial hydrogenation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/885—Molybdenum and copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/24—Chromium, molybdenum or tungsten
- C07C2523/28—Molybdenum
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/72—Copper
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/74—Iron group metals
- C07C2523/755—Nickel
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
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Abstract
The invention relates to an improved method for producing a substituted or unsubstituted phenylcyclohexane by catalytically hydrogenating a substituted or unsubstituted biphenyl.
Description
Describe
The present invention relates to a kind of improved by replacing or unsubstituted biphenyl carries out catalytic hydrogenation prepare the method for replacement or unsubstituted Santosol 360.
The perhydro-of having known a phenyl ring by biphenyl in principle prepares Santosol 360.
Formed by product especially comprises the connection hexanaphthene usually, and itself and Santosol 360 form azeotrope.
At Journal of Chemical Society1951, in the 1371-1372 page or leaf, I.Goodman described by biphenyl in ethanol in the presence of Raney nickel catalytic hydrogenation become Santosol 360 to prepare the method for Santosol 360.
Tetrahedron Letters2000, No.41,5865-5868 page or leaf have described by biphenyl and have carried out hydrogenation in the presence of Raney nickel-aluminium alloy to prepare the method for Santosol 360 under the temperature of 90 ° of C.
DE937950 discloses that a kind of use is not nickeliferous to become the biphenyl catalytic hydrogenation method of Santosol 360 with the copper-chromium catalyst that does not contain cobalt under the temperature of about 240-260 ° C.
US3387048 discloses a kind of by under the situation of adding the solvent hexanaphthene biphenyl being carried out hydrogenation to prepare the method for Santosol 360.Appropriate catalyst is 5% a batch of palladium carbon.
DE2125473 relates to and contains cobalt oxide or cobalt oxide mixture, for example Co
3O
4Be used for the partial hydrogenation of biphenyl derivatives with the catalyzer of CoO.
WO93/16972 relate to be used for many rings and monocyclic aromatic substance for example the biphenyl of the benzene derivative of alkyl replacement and replacement carry out the catalyzer of hydrogenation, wherein this catalyzer contains ruthenium.
CN1800121 discloses a kind of method for preparing Santosol 360, wherein hydrogenation biphenyl in the presence of nickel-aluminum catalyst.
EP0394842 relates to the catalyzer that is used for the Hydrogenated aliphatic unsaturated compound, wherein this catalyzer contains nickel and copper, it is characterized in that containing the nickel oxide of 20-75 weight %, the zirconium dioxide of 10-75 weight % and the cupric oxide of 5-50 weight %, in each case based on unreduced oxide catalyst meter.This catalyzer is particularly suitable for hydrogenation at industrial important compound 2-butyne-1,4-glycol, 2-butylene-1,4-two pure and mild 2-ethyl hexene-2-aldehyde.
A part is above-mentioned to be prepared and replaces or the method for unsubstituted Santosol 360 is used be not easy the catalyzer handling or be not easy to obtain on technical scale.In addition, known method shows for the selectivity of target product unsatisfactory in some cases, and/or space-time yield is low excessively.
Based on prior art, the purpose of this invention is to provide the method that can under the condition of economic optimization, prepare Santosol 360 by the hydrogenation of biphenyl.This method should be on technical scale carrying out in controllable mode aspect the process engineering, and can use cheap catalyzer to obtain required product with required high chemical yield and highly selective.The formation of connection hexanaphthene should be avoided as much as possible, because as indicated above, connection hexanaphthene and Santosol 360 form azeotrope, and this has reduced the productive rate of purified petroleum benzin basic ring hexane in distillation is purified.
This purpose realizes by the replacement of a kind of preparation formula I or the method for unsubstituted Santosol 360:
Replacement or the unsubstituted biphenyl of its Chinese style II carry out catalytic hydrogenation in the presence of hydrogen and catalyzer,
R wherein
1Be hydrogen and R
2Be hydrogen or phenyl, or R
1Be C
1-C
4-alkyl and R
2Be hydrogen, or R
1And R
2Be identical and each phenyl or identical C naturally
1-C
4-alkyl, wherein R
1And R
2All be positioned at corresponding ortho position, a position or the contraposition of two phenyl ring of formula II biphenyl simultaneously,
Described catalyzer contains:
The oxygenatedchemicals of the nickel of-30-70 weight % calculates as NiO,
The oxygenatedchemicals of the zirconium of-15-45 weight % is as ZrO
2Calculate,
The oxygenatedchemicals of the copper of-5-30 weight % calculates as CuO,
The oxygenatedchemicals of the molybdenum of-0.1-10 weight % is as MoO
3Calculate and
Other component of-0-10 weight %,
Wherein wt % data are based on the unreduced catalyzer meter of exsiccant.
In the methods of the invention, the biphenyl of formula II is used as raw material,
R wherein
1Be hydrogen and R
2Be hydrogen or phenyl, or R
1Be C
1-C
4-alkyl and R
2Be hydrogen, or R
1And R
2Be identical and each phenyl or identical C naturally
1-C
4-alkyl, wherein R
1And R
2All be positioned at corresponding ortho position, a position or the contraposition of two phenyl ring of formula II biphenyl simultaneously.
C
1-C
4-alkyl is methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, the tertiary butyl or 2-methyl isophthalic acid-propyl group, the preferable methyl or the tertiary butyl, particularly methyl.
The example of formula II biphenyl is especially:
The preferably unsubstituted biphenyl of the biphenyl of formula II, i.e. R
1And R
2Each is hydrogen naturally.
So preferred a kind of the invention described above method, wherein R
1And R
2Be hydrogen, i.e. the method for the Santosol 360 of a kind of preparation formula Ia:
Wherein the unsubstituted biphenyl with formula IIa carries out catalytic hydrogenation
The biphenyl of formula II that can be used for the inventive method is normally commercially available, for example the simple biphenyl that obtains from the distilled oil of hard coal tar.The biphenyl that replaces can be for example by well known to a person skilled in the art that the aryl-aryl linked reaction obtains for example Suzuki coupling.
The inventive method is carried out in the presence of hydrogen and in the presence of heterogeneous catalyst, and wherein used heterogeneous catalyst contains: the oxygenatedchemicals of the nickel of 30-70 weight %, preferred 40-60 weight %, calculate as NiO; The oxygenatedchemicals of the zirconium of 15-45 weight %, preferred 20-40 weight % is as ZrO
2Calculate; The oxygenatedchemicals of the copper of 5-30 weight %, preferred 10-25 weight % calculates as CuO; With the oxygenatedchemicals of the molybdenum of 0.1-10 weight %, preferred 0.5-5 weight %, as MoO
3Calculate, randomly with other component of 0-10 weight %, preferred 0-5 weight %, graphite for example.Here, weight % data are based on the unreduced catalyzer meter of exsiccant.
Because described concentration is based on the catalytic activity composition of catalyzer except as otherwise noted separately, so the catalytic activity composition of catalyzer will be defined as after last thermal treatment and before with hydrogen reducing hereinafter, in catalyzer as the quality summation of zirconium, nickel, copper and the molybdenum of catalytic active component, in each case correspondingly as ZrO
2, NiO, CuO and MoO
3Calculate.
In a preferred embodiment, the inventive method uses the catalyzer that contains following component to carry out:
The oxygenatedchemicals of the nickel of-45-55 weight % calculates as NiO,
The oxygenatedchemicals of the zirconium of-25-35 weight % is as ZrO
2Calculate,
The oxygenatedchemicals of the copper of-13-20 weight % calculates as CuO,
The oxygenatedchemicals of the molybdenum of-1-3 weight % is as MoO
3Calculate and
Other component of-0-5 weight %,
The summation of wherein wt % data is 100 weight % and is based on the unreduced catalyzer meter of exsiccant.According to the present invention, very particularly preferably by said components according to shown in the catalyzer formed of part by weight.
The catalyzer that very particularly preferably is used for the inventive method contains the NiO of 49-53 weight %, the CuO of 15-19 weight %, the ZrO of 28-32 weight %
2, the MoO of 1-2 weight %
3Randomly other component, for example graphite of 0-3 weight %, wherein the part by weight of selecting for each component in each case is based on the unreduced catalyzer of exsiccant, and summation is 100 weight %.These catalyzer are known, for example can be as preparation as described in the EP0696572.
Catalyzer that can be used according to the invention can be for example by using the intermediate processing preparation.Therefore, for example they can by nickel and copper component from the aqueous salts solution that contains these elements with mineral alkali co-precipitation in the presence of the oxygenatedchemicals of the zirconium of microsolubility come out, subsequently the throw out that is obtained washed, dry and calcining obtains.Oxygenatedchemicals as the zirconium of microsolubility can use for example zirconium dioxide, Zirconium oxide hydrate, zirconium phosphate, boric acid zirconium and zirconium silicate.The slurries of microsolubility zirconium compounds can prepare in water at the vigorous stirring low suspension by the fine powder with these compounds.These slurries are advantageously by being precipitated out acquisition with mineral alkali from the aqueous solution of zirconates with the microsolubility zirconium compounds.
Catalyzer that can be used according to the invention preferably prepares by the co-precipitation (mixed precipitation) of all its components.For this purpose, the aqueous salts solution that will contain catalyst component advantageously mixes with inorganic base aqueous solution in heating with when stirring, and finishes up to precipitation, and mineral alkali is alkali metal base especially, for example yellow soda ash, sodium hydroxide, salt of wormwood or potassium hydroxide.The type of used salt generally is not crucial; Because the water-soluble of salt is important in this operation, standard is required good water-soluble of salts solution of these higher concentrations of preparation.Think that clearly when selecting the salt of each component, only have not can the anionic salt of interferential in selection certainly, no matter described interference promptly is by causing unwanted precipitation or owing to forming title complex and cause the precipitation difficulty or stop fully precipitating.
The catalyzer of can be used according to the invention and having a particularly advantageous performance can obtain by a part of zirconium component of precipitated catalyst, and advantageously from the aqueous solution precipitation of zirconates, this is undertaken by adding aqueous mineral alkali in settler individually.All the other zirconium components of catalyzer can be deposited on the new sedimentary Zirconium oxide hydrate in above-mentioned co-precipitation gained, preferred then with other catalytic active component.Here, generally finding particularly advantageous is the 10-80 weight % that is deposited in the zirconium total amount in the catalytic activity composition, preferred 30-70 weight %, especially 40-60 weight %.
The throw out that obtains in these precipitin reaction chemically is being uneven usually, and especially contains the mixture of oxide compound, hydrous oxide, oxyhydroxide, carbonate and insoluble and the basic salt of above-mentioned metal.Discovery is advantageously aging with throw out aspect sedimentary filterableness, is about to it and leaves standstill for some time after precipitation, randomly carries out under heating state or under the situation that air is passed through.
Can further process in a conventional manner by the throw out that these intermediate processings obtain, obtain can be used according to the invention catalyzer.After washing, they are generally dry under 80-200 ° of C, preferred 100-150 ° of C, calcining then.Calcining is carried out under the temperature of 300-800 ° of C usually, preferred 400-600 ° of C, especially 450-550 ° C.
After calcining, catalyzer is advantageously regulated, and this makes it reach specific particle diameter by grinding to carry out, or by with its after grinding with shaping assistant for example graphite or stearic acid mix and carry out, be pressed into molding with tabletting machine, and heat-treat.The temperature here is generally corresponding to the temperature in the calcining.
The contained catalytically-active metals of Zhi Bei catalyzer is the form of mixture of their oxygenatedchemicals in this way, promptly especially as oxide compound and blended oxide compound.
Zhi Bei catalyzer can store with former state and use in this way.As before the catalyzer, they carry out prereduction usually in the methods of the invention.But they also can use under the situation of prereduction not having, in this case they then under according to the condition of hydrogenation of the present invention with the hydrogen reducing that is present in the reactor.For prereduction, catalyzer is exposed to nitrogen/hydrogen atmosphere earlier usually and reaches 12-20 hour under 150-200 ° of C, handles then to reach about 24 hours in hydrogen atmosphere under 200-300 ° of C.In prereduction, the part of the metal oxygen-containing compound that exists in catalyzer is reduced into corresponding metal usually, makes them exist with the activity of such catalysts form with various oxygen compounds.
Generally, catalyzer used according to the invention preferably uses with the form of full active catalyst.Term " complete active " the such catalyzer of expression, it is compared with the catalyzer of load, is made up of the catalytic activity composition fully.Full active catalyst can be introduced in the reaction vessel by the catalytic activity composition of grind into powder and use, or by the catalytic activity composition is packed into after grinding, mixes with shaping assistant, moulding and as molded catalyst bodies thermal treatment in reactor use, molded catalyst bodies for example is ball, right cylinder, pellet, ring, spirochete, extrudate etc.
In a preferred embodiment of the inventive method, selected catalyzer is a heterogeneous catalyst, is used for catalytic hydrogenation with the form of fixed bed catalyst, promptly is used for the step of hydrogenation of the inventive method.
In order to carry out the inventive method, above-mentioned raw materials, promptly the biphenyl of formula II contacts with selected catalyzer with hydrogen.Hydrogen can use with undiluted form, and purity is about 99 volume % usually, or uses with the form of dilution, promptly with the rare gas element form of the mixture of argon gas or nitrogen for example.Hydrogen preferably uses with undiluted form.
Catalytic activity hydrogenation can under the situation of not adding solvent or reaction conditions is being organic solvent inert in the presence of successfully carry out, described organic solvent for example is methyl alcohol, ethanol, Virahol, hexane, heptane, hexanaphthene etc.Hydrogenation preferably carries out under the situation of not adding solvent.
In the methods of the invention, the hydrogenation of formula II biphenyl can cling at 1-200 under the hydrogen pressure of (absolute value) and carry out, preferred 2-150 crust, preferred especially 4-80 crust, very particularly preferably 5-50 crust.As being used to carry out the hydrogenant temperature of reaction, the favourable temperature that is chosen in the 50-250 ° of C scope, preferred 100-180 ° of C, very particularly preferably 110-160 ° of C.
In technical scale, this method is supplied to catalyzer to carry out by the formula II biphenyl that will react usually, described catalyzer is present in the fixed-bed reactor of preferred outer heating usually, and for example tubular reactor, autoclave or shell and tube-type reactor are under required temperature of reaction and required pressure.Here, usually to the formula II biphenyl of catalyzer supply 0.1-1.0kg, preferred 0.1-0.6kg and preferred especially 0.2-0.4kg, and per hour by every kg catalyzer.Here, the formula II biphenyl that can advantageously will use heated before adding reaction vessel or reactor, preferably was heated to temperature of reaction.
Reactor can be according to the operation of upflow mode or downflow mode, and promptly raw material can pass through reactor according to from bottom to top form or form from the top down.Step of hydrogenation in the inventive method can intermittently or be carried out continuously.In both cases, unreacted raw material can circulate with hydrogen.
Step of hydrogenation in the inventive method also can be carried out in the cascade of a plurality of reactors that are connected in series step by step, promptly common 2-4, preferred 2 or 3, preferred especially 2 reactors, preferred fixed-bed reactor.Here, the main conversion of reaction realizes under above-mentioned reaction conditions that in first reactor this reactor is commonly referred to main reactor; The crude product that is obtained is delivered in second reactor, and this reactor is commonly referred to post-reactor, and still unreacted here raw material is converted to the Santosol 360 of formula I at least basically according to the present invention.Here, reaction conditions can be selected independently of one another, preferably selects in above-mentioned scope.
In the methods of the invention, hydrogenation can be intermittently, semicontinuous or all carry out continuously.Catalytic hydrogenation is in the methods of the invention preferably carried out continuously, especially all carries out continuously, wherein raw material is introduced in the reactor continuously, and the reaction mixture or the reaction product of gained are discharged from reactor continuously.
Reaction mixture that obtains in the step of hydrogenation of the inventive method or reaction product can be carried out in container after the intermediate buffering, purify by fractionation, preferably under reduced pressure carry out fractionation, thus obtain purity based on the gross weight meter greater than 97 weight %, be preferably greater than replacement or the unsubstituted Santosol 360 of the formula I of 98 weight %.Can intermittently or in the rectifying tower of operate continuously carry out by the aftertreatment that distillation is carried out the gained reaction product.Described the various industrial implementation schemes of this distillation tower in pertinent literature, it allows intermittently, the distillation of semicontinuous or whole successive.
Therefore, a preferred embodiment of the inventive method is included in the reaction product of gained in the catalytic hydrogenation and handles by distilling in another processing step, thus the replacement of the formula I that further purifies or unsubstituted Santosol 360.
Various process programs are the continuous fractionation that are used for multicomponent mixture according to the prior art routine.Under the simplest situation, incoming mixture is separated into two cuts, i.e. lower boiling overhead fraction and high boiling point tower bottom distillate.When incoming mixture is separated into more than two kinds of cuts, in this process program, must use a plurality of distillation towers.In order to be limited in the cost of device aspect, use tower with the side discharging that is used for liquid or steam, wherein can carry out the fractionation of multicomponent mixture.But the restriction of using distillation tower with side discharging to be subjected to a great extent is that the product that takes out in the side discharging can not be fully pure according to prior art forever.Under the situation of the side discharging in the enrichment section, wherein product takes out with liquid form usually, the side product still contain a certain proportion of should be at the top isolating low boiling component.Similar situation is applicable to the side discharging in stripping stage, and wherein product takes out with the steam form usually, and the side product still has a certain proportion of high boiling product in this case.So the use of conventional side discharging tower is subject to the situation that can allow contaminated side product.
A kind of possible compensation way is to provide by the spaced walls tower.This tower is for example referring to US2, and 471,134; US4,230,533; EP0122367; EP0126288; EP0133510; Chem.Eng.Technol.10 (1987) 92 – 98; Chem.-Ing.-Tech.61 (1989) No.1,16 – 25; Gas delivery and purification (Gas Separation and Purification) 4 (1990) 109 – 114; Process engineering (Process Engineering) 2 (1993) 33 – 34; Trans IChemE72 (1994) Part A639 – 644 and chemical engineering (Chemical Engineering) 7 (1997) 72 – 76.
Advantageously under reduced pressure under the absolute pressure of 1-100 millibar, carry out preferred 5-50 millibar from the post-processing operation that the reaction product of catalytic hydrogenation is undertaken by distillation.Under the situation of underpressure distillation, the preferred distillation tower that uses with orderly gauze packing, described filler has 250-1000m
2/ m
3Specific surface area.
The intermittent fractionation that the reaction discharging that obtains from biphenyl is carried out, its discharging has comprised unwanted over-hydrogenation product connection hexanaphthene, the connection hexanaphthene is accompanied by the required Santosol 360 of remarkable ratio, with its formation lower boiling azeotrope, described hexanaphthene can be separated in one or more low boiler cuts.If the connection hexanaphthene distills away from still kettle, then can obtain the pure fraction with middle boiling point of Santosol 360.Unreacted raw material biphenyl is retained at the bottom of the tower, and wherein a part also can be distilled away, and this depends on amount and process environments.
Can advantageously use this hydrogenation that is used for carrying out in industrial implementation, be not the conversion fully that proceeds to biphenyl, but in case find that occurring joining hexanaphthene in the reaction discharging first just disturbs.This can for example be undertaken by the limited reactions time under the situation of rhythmic reaction, or under the situation of successive reaction, undertaken by conditioned reaction actuator temperature or hydrogenation pressure, promptly control conversion of raw material by conditioned reaction temperature and/or reaction pressure and/or the residence time of reaction soln in hydrogenation equipment.
In a preferred embodiment of the inventive method, carry out hydrogenation so that the replacement of the formula II of 90-95% or unsubstituted biphenyl react.
The bottom materials that is rich in biphenyl that keeps after fractionation can be recycled in the reaction, makes the overall yield of Santosol 360 improve.
In a particularly preferred form of the inventive method, will be recycled in the hydrogenation whole or in part the cut that carries out obtaining in the aftertreatment from the reaction product of catalytic hydrogenation and still contain formula II biphenyl by distillation.
Below by embodiment the present invention is described, but does not limit the present invention.
Embodiment
All experiments are carried out in the HC laboratory autoclave with catalyzer bucket of 300ml.Can be via the pipe sampling that connects at sidepiece.Temperature regulation is undertaken by outside oil bath.
Analyze
GC analyzes and carries out by the following method: 30m DB-WAX, ID.:0.2mm, FD.0.5 μ m, initial temperature: 200 ° of C, detected temperatures: 250 ° of C; Began-200 ° of 3 ° of 80 ° of C – C/ minute C/15 minute; 240 ° of C/20 minute isothermals; Injection volume: 0.2 μ l; Carrier gas He; t
R=minute; t
R(biphenyl): 25.6; t
R(Santosol 360): 15.4; t
R(benzyl ring hexene): 10.2,10.6 and 11.0; t
R(connection hexanaphthene): 8.7.
Embodiment 1
In the 300ml laboratory autoclave, with biphenyl hydrogenation in the presence of the 5g catalyzer of 99.6g, described catalyzer contains the CuO of NiO, the 17 weight % of 50 weight %, the ZrO of 30.5 weight %
2MoO with 1.5 weight %
3And be the pellet form with diameter and height of 3mm in each case, described hydrogenation is carried out when stirring under the temperature of 30 hydrogen pressures that cling to and 130 ° of C.After 22 hours reaction times, filter out catalyzer.Analyze by gas-chromatography at the reaction mixture that time obtained shown in the table 1.The results are shown in the table 1.
Table 1
Embodiment 2
In the 300ml laboratory autoclave, with biphenyl hydrogenation in the presence of the 5g catalyzer of 100g, described catalyzer contains the CuO of NiO, the 17 weight % of 50 weight %, the ZrO of 30.5 weight %
2MoO with 1.5 weight %
3And be the pellet form with diameter and height of 3mm in each case, described hydrogenation is carried out when stirring under the temperature of 40 hydrogen pressures that cling to and 130 ° of C.After 14 hours reaction times, filter out catalyzer.Analyze by gas-chromatography at the reaction mixture that time obtained shown in the table 2.The results are shown in (in each case, unit is GC area %) in the table 2.
Table 2
Embodiment 3
In the 300ml laboratory autoclave, with biphenyl hydrogenation in the presence of the 5g catalyzer of 100g, described catalyzer contains the CuO of NiO, the 17 weight % of 50 weight %, the ZrO of 30.5 weight %
2MoO with 1.5 weight %
3And be the pellet form with diameter and height of 3mm in each case, described hydrogenation is carried out when stirring under the temperature of 10 hydrogen pressures that cling to and 150 ° of C.After 17 hours reaction times, filter out catalyzer.Analyze by gas-chromatography at the reaction mixture that time obtained shown in the table 3.The results are shown in (in each case, unit is GC area %) in the table 3.
Table 3
Embodiment 4
In the 300ml laboratory autoclave, with biphenyl hydrogenation in the presence of the 5g catalyzer of 100g, described catalyzer contains the CuO of NiO, the 17 weight % of 50 weight %, the ZrO of 30.5 weight %
2MoO with 1.5 weight %
3And be the pellet form with diameter and height of 3mm in each case, described hydrogenation is carried out when stirring under the temperature of 10 hydrogen pressures that cling to and 130 ° of C.After 48 hours reaction times, filter out catalyzer.Analyze by gas-chromatography at the reaction mixture that time obtained shown in the table 4.The results are shown in (in each case, unit is GC area %) in the table 4.
Table 4
The comparative example 5
In the 300ml laboratory autoclave, with the 20g biphenyl hydrogenation in the presence of the 5g catalyzer that is dissolved in the 80g methyl alcohol, described catalyzer contains at Al
2O
30.5%Ru on the carrier and be the form of 4-6mm ball, described hydrogenation is carried out when stirring under the temperature of the hydrogen pressures of 30 crust and 90-120 ° of C.After 12 hours reaction times, filter out catalyzer.Analyze by gas-chromatography at the reaction mixture that time obtained shown in the table 5.The results are shown in (in each case, unit is GC area %) in the table 5.
Table 5
The comparative example 6
In the 300ml laboratory autoclave, with the hydrogenation in the presence of the 5g catalyzer of 100g biphenyl, described catalyzer contains at Al
2O
30.5%Ru on the carrier and be the form of 4-6mm ball, described hydrogenation is carried out when stirring under the temperature of the hydrogen pressures of 30 crust and 120 ° of C.After 14.5 hours reaction times, filter out catalyzer.Analyze by gas-chromatography at the reaction mixture that time obtained shown in the table 6.The results are shown in (in each case, unit is GC area %) in the table 6.
Table 6
The comparative example 7
In the 300ml laboratory autoclave, with the hydrogenation in the presence of the 5g catalyzer of 100g biphenyl, described catalyzer contains at SiO
2On 0.3%Ru and be the form of 4-6mm ball, described hydrogenation is carried out when stirring under the hydrogen pressures of 40 crust and the temperature of 130 ° of C.After 5 hours reaction times, filter out catalyzer.Analyze by gas-chromatography at the reaction mixture that time obtained shown in the table 7.The results are shown in (in each case, unit is GC area %) in the table 7.
Table 7
The comparative example 8
In the 300ml laboratory autoclave, with the hydrogenation in the presence of the 5g catalyzer of 100g biphenyl, described catalyzer contains at SiO
2On Ru, be at SiO
2On 0.3%Ru and be the form of 4-6mm ball, described hydrogenation is carried out when stirring under the hydrogen pressures of 10 crust and the temperature of 90 ° of C.After 23 hours reaction times, filter out catalyzer.Analyze by gas-chromatography at the reaction mixture that time obtained shown in the table 8.The results are shown in (in each case, unit is GC area %) in the table 8.
Table 8
Embodiment 9 distillation crude benzol basic ring hexanes
Table 9 is presented at the result who distills thick discharging in the long distillation tower of 100cm according to the batch distillation mode; described thick discharging has following composition: 80.9% Santosol 360,18.3% connection hexanaphthene and 0.86% biphenyl are (in each case; unit is GC weight %), described distillation tower is the rotation belt tower (about 20 theoretical trays) of protected property heating.This device is equipped with heart-shaped flask of the double-walled of the 0.1L that is positioned at the bottom and vapor distribution device.Vapour pipe at the top heats by the heating zone, and condenser is operated under 2 ° of C.Product mixtures is according to the reflux ratio fractionation of 5:1.In order to contrast, table 10 be presented at have 94.3% Santosol 360,5.2% hexanaphthene and contain remarkable less hexanaphthene (in each case, unit is GC weight %) the distillation of discharging in the result that obtains, obtain significantly relatively large Santosol 360 up to specification.
For the Santosol 360 with low levels connection hexanaphthene is provided, in distillation tower DN50, carry out the successive experiment, distillation tower DN50 is equipped with the Sulzer DX filler (about 48 theoretical trays) of the 2.4m that has an appointment and operates under 10 millibars top pressure.
The product that obtains at the bottom of tower contains in each case and surpasses 98% Santosol 360, wherein joins cyclohexane concentration in the 0.2-0.7% scope.The connection hexanaphthene content of overhead product is 19-50%, along with reflux ratio (4:1-19:1) changes.Under higher reflux ratio (11:1 and Geng Gao), can reach 90% distillation productive rate.
Table 9: the batch distillation of Santosol 360
Table 10: the batch distillation of Santosol 360
Claims (11)
1. the method for the replacement of a preparation formula I or unsubstituted Santosol 360:
Replacement or the unsubstituted biphenyl of its Chinese style II carry out catalytic hydrogenation in the presence of hydrogen and catalyzer,
R wherein
1Be hydrogen and R
2Be hydrogen or phenyl, or R
1Be C
1-C
4-alkyl and R
2Be hydrogen, or R
1And R
2Be identical and each phenyl or identical C naturally
1-C
4-alkyl, wherein R
1And R
2All be positioned at corresponding ortho position, a position or the contraposition of two phenyl ring of formula II biphenyl simultaneously,
Described catalyzer contains:
The oxygenatedchemicals of the nickel of-30-70 weight % calculates as NiO,
The oxygenatedchemicals of the zirconium of-15-45 weight % is as ZrO
2Calculate,
The oxygenatedchemicals of the copper of-5-30 weight % calculates as CuO,
The oxygenatedchemicals of the molybdenum of-0.1-10 weight % is as MoO
3Calculate and
Other component of-0-10 weight %,
Wherein wt % data are based on the unreduced catalyzer meter of exsiccant.
2. the process of claim 1 wherein R
1And R
2Each is hydrogen naturally.
3. claim 1 or 2 method, wherein use the catalyzer that contains following component:
The oxygenatedchemicals of the nickel of-45-55 weight % calculates as NiO,
The oxygenatedchemicals of the zirconium of-25-35 weight % is as ZrO
2Calculate,
The oxygenatedchemicals of the copper of-13-20 weight % calculates as CuO,
The oxygenatedchemicals of the molybdenum of-1-3 weight % is as MoO
3Calculate and
Other component of-0-5 weight %,
The summation of wherein wt % data is 100 weight % and is based on the unreduced catalyzer meter of exsiccant.
4. each method among the claim 1-3, wherein catalyzer uses with the form of fixed bed catalyst.
5. each method among the claim 1-4, wherein hydrogenation clings under the absolute hydrogen pressure at 4-80 and carries out.
6. each method among the claim 1-5, wherein hydrogenation carries out under 100-180 ℃ temperature.
7. each method among the claim 1-6, wherein catalytic hydrogenation is carried out continuously.
8. each method among the claim 1-7, wherein in another processing step, the reaction product that obtains in catalytic hydrogenation is carried out replacement or the unsubstituted Santosol 360 of aftertreatment with further purification formula I by distillation.
9. the method for claim 8 is under reduced pressure to carry out under the absolute pressure of 1-100 millibar to the aftertreatment of being undertaken by distillation from the reaction product of catalytic hydrogenation wherein.
10. claim 8 or 9 method wherein will be recycled in the hydrogenation the cut that carries out obtaining in the aftertreatment from the reaction product of catalytic hydrogenation and still contain formula II biphenyl whole or in part by distillation.
11. each method among the claim 1-10 is wherein carried out hydrogenation so that the replacement of the formula II of 90-95% or unsubstituted biphenyl react.
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EP10189628 | 2010-11-02 | ||
EP10189628.0 | 2010-11-02 | ||
PCT/EP2011/068810 WO2012059387A1 (en) | 2010-11-02 | 2011-10-27 | Method for the production of a phenylcyclohexane |
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JP (1) | JP5784742B2 (en) |
CN (1) | CN103228601B (en) |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104402662A (en) * | 2014-12-15 | 2015-03-11 | 常熟市新腾化工有限公司 | Method for preparing phenylcyclohexane |
CN104447170A (en) * | 2014-12-15 | 2015-03-25 | 常熟市新腾化工有限公司 | Preparation method of cyclohexylbenzene |
CN105016957A (en) * | 2014-11-03 | 2015-11-04 | 江苏苏化集团有限公司 | Method for preparing phenylcyclohexane through biphenyl catalytic hydrogenation |
CN107185548A (en) * | 2017-06-07 | 2017-09-22 | 中国石油大学(华东) | A kind of method that biphenyl selective hydrogenation prepares cyclohexyl benzene |
Families Citing this family (1)
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DE112013004901A5 (en) | 2012-10-04 | 2015-07-02 | Basf Se | Process for the preparation of phenylcyclohexane |
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- 2011-10-27 CN CN201180057493.7A patent/CN103228601B/en not_active Expired - Fee Related
- 2011-10-27 EP EP11776160.1A patent/EP2635544B1/en not_active Not-in-force
- 2011-10-27 JP JP2013537073A patent/JP5784742B2/en not_active Expired - Fee Related
- 2011-10-27 MX MX2013004872A patent/MX2013004872A/en active IP Right Grant
- 2011-10-27 WO PCT/EP2011/068810 patent/WO2012059387A1/en active Application Filing
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CN105016957A (en) * | 2014-11-03 | 2015-11-04 | 江苏苏化集团有限公司 | Method for preparing phenylcyclohexane through biphenyl catalytic hydrogenation |
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CN107185548A (en) * | 2017-06-07 | 2017-09-22 | 中国石油大学(华东) | A kind of method that biphenyl selective hydrogenation prepares cyclohexyl benzene |
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EP2635544B1 (en) | 2014-12-17 |
EP2635544A1 (en) | 2013-09-11 |
ES2532540T3 (en) | 2015-03-27 |
MX2013004872A (en) | 2013-05-22 |
JP2014501706A (en) | 2014-01-23 |
WO2012059387A1 (en) | 2012-05-10 |
JP5784742B2 (en) | 2015-09-24 |
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